Effects of External Ions upon Proton Transfer Reactions. H-Bonded Systems Containing HCOOH
International Journal of Quantum Chemistry
Ab initio calculations reveal that a cation, in a position equidistant from the two H-bonding oxygen atoms of (HC(OH)O · H · OH2)+, acts to push the proton from HCOOH toward OH2 if the ion is located near the —OH or CH group of HCOOH. In contrast, rotation of the cation out of the HCOOH plane, while maintaining its position relative to the two H-bonding atoms, leads to a potential which is little different than that observed in the absence of an ion. These findings are readily explained on the basis of ion-induced internal polarization of the subunit to which the ion is closer. Replacement of OH2 by HCOOH suggests that polarization of the more distant subunit can also be a factor.
Effects of External Ions upon Proton Transfer Reactions. H-Bonded Systems Containing HCOOH S. Scheiner and T. Das Int. J. Quantum Chem., 1988 34, Issue S15, 137-147.